CN107522276B - Preparation method of water defluorinating agent - Google Patents
Preparation method of water defluorinating agent Download PDFInfo
- Publication number
- CN107522276B CN107522276B CN201710867027.4A CN201710867027A CN107522276B CN 107522276 B CN107522276 B CN 107522276B CN 201710867027 A CN201710867027 A CN 201710867027A CN 107522276 B CN107522276 B CN 107522276B
- Authority
- CN
- China
- Prior art keywords
- waste
- waste concrete
- set cement
- water body
- concrete
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000002699 waste material Substances 0.000 claims abstract description 61
- 239000011737 fluorine Substances 0.000 claims abstract description 51
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 51
- 239000004567 concrete Substances 0.000 claims abstract description 49
- 239000004568 cement Substances 0.000 claims abstract description 46
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000002245 particle Substances 0.000 claims abstract description 20
- 238000001354 calcination Methods 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 15
- 238000000498 ball milling Methods 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 238000010276 construction Methods 0.000 claims description 12
- 230000000694 effects Effects 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 10
- 230000007547 defect Effects 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 229920001732 Lignosulfonate Polymers 0.000 claims description 4
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 3
- 230000000704 physical effect Effects 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 3
- 239000002351 wastewater Substances 0.000 abstract description 15
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000012216 screening Methods 0.000 abstract description 2
- 231100000419 toxicity Toxicity 0.000 abstract description 2
- 230000001988 toxicity Effects 0.000 abstract description 2
- -1 fluorine ions Chemical class 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000006115 defluorination reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 235000012241 calcium silicate Nutrition 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 208000004998 Abdominal Pain Diseases 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 206010028813 Nausea Diseases 0.000 description 1
- 208000007107 Stomach Ulcer Diseases 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000007059 acute toxicity Effects 0.000 description 1
- 231100000403 acute toxicity Toxicity 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 208000022531 anorexia Diseases 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 206010061428 decreased appetite Diseases 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910001653 ettringite Inorganic materials 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000037406 food intake Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000008693 nausea Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/583—Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing fluoride or fluorine compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a preparation method of a water body fluorine removal agent, which comprises the steps of taking waste concrete as a raw material, carrying out primary crushing and calcination, screening set cement, carrying out powder selection and separation on the set cement after ball milling, and collecting particles with the particle size of below 80 mu m to obtain the water body fluorine removal agent. The water body defluorinating agent is prepared from the waste concrete, the raw materials are wide in source and low in cost, and a new way is provided for resource utilization of the waste concrete; also provides a process method which is simple and convenient to operate, wide in application range, low in cost, green and environment-friendly and can treat toxicity by waste for the treatment of fluoride-containing wastewater of rivers, lakes, industry, life and the like in China; the resource utilization efficiency of the waste set cement is improved, and a technical path is provided for the high value-added utilization of the hardened set cement in the waste concrete.
Description
Technical Field
The invention belongs to the field of waste resource utilization, and particularly relates to a preparation method of a water body defluorinating agent.
Background
A large amount of construction waste can be generated in construction industry activities such as construction, decoration, removal and the like of buildings or structures, and the generation amount of the construction waste is continuously increased along with the rapid promotion of infrastructure and the acceleration of urbanization rate in China. According to statistics, 1/3 in the urban garbage is about building garbage; the stock of the building garbage is over 20 hundred million tons by the end of 2011, and over 3 hundred million tons of building garbage are newly added every year. Because the site selection of the building garbage landfill plants in most cities is improper or the plants are stacked temporarily, not only is a great deal of waste of land resources caused, but also great potential safety hazards exist. Meanwhile, the construction waste interacts with water in the surrounding environment during the stacking and landfill processes, and leachate of the construction waste can pollute surface water or underground water.
The waste concrete is an important part of the construction waste and accounts for about 34 percent of the total amount of the construction waste. But the resource utilization rate of the waste concrete in China is less than 5 percent. At present, the main resource utilization approach is to prepare recycled concrete aggregate, but a large amount of hardened set cement is adhered to the surface of the recycled aggregate, and due to the high porosity, the water absorption and the low strength of the hardened set cement, the mechanical property of the recycled aggregate is reduced, the workability of the recycled concrete is poor, and the volume stability of the hardened set cement is deteriorated. Therefore, a large amount of hardened set cement in the waste concrete becomes a main factor for restricting the preparation of the recycled aggregate from the waste concrete.
At present, resource utilization research on hardened set cement in waste concrete is relatively lacked, and most of the research is focused on the field of preparing building materials, such as building blocks or cement preparation through calcination again. However, the waste set cement has high porosity, high water requirement for thickening, low activity index and limited mixing amount in the use process, and the building material product prepared by the waste set cement has poor construction performance and mechanical property. Meanwhile, because the gelling matrix separated from the waste concrete contains a certain amount of inert silicon dioxide, the difficulty is brought to the grinding of cement raw materials and the calcination of clinker, the content of f-CaO in the clinker is increased, the quality of the clinker is reduced, and the production cost is increased.
Fluorine is one of trace elements necessary for maintaining normal life activities of human bodies, is also an important industrial raw material, and has wide application in the fields of chemical fertilizers, metallurgy, aerospace, refrigeration, organic synthesis, integrated circuits, glass and the like. In the application, a large amount of fluorine-containing wastewater is inevitably generated, and if the fluorine-containing wastewater is not treated well, not only is environmental pollution generated, but also the health of human beings is threatened finally. For example, a small amount of fluorine (up to 150 mg) can cause a series of ailments, and ingestion of more fluorine-containing compounds in humans can cause acute toxicity. Depending on the intake, various conditions may arise, such as anorexia, nausea, abdominal pain, gastric ulcers, cramped bleeding and even death.
The current common methods for treating fluorine-containing wastewater include chemical precipitation, adsorption, coagulation and sedimentation, reverse osmosis, ion exchange, electrochemical treatment, and the like. Among the numerous treatment methods, the chemical precipitation method, the adsorption method and the coagulation sedimentation method are the most important technical method for treating the fluorine-containing wastewater at present due to the advantages of stable treatment effect, simple process, low operation cost, large treatment capacity, suitability for treating high-concentration fluorine-containing wastewater and the like.
The precipitation method and the adsorption method mainly depend on adding a large amount of chemical agents to form fluoride precipitates or fluoride is adsorbed on the surfaces of precipitates to form coprecipitation in the treatment process, or remove fluorine ions in water in a physical and chemical adsorption mode, and finally remove the fluorine ions in the water in a solid-liquid separation mode. Since the entire process requires the use of large amounts of chemicals, the cost of chemicals becomes a significant source of the overall process cost. Therefore, the development of new, less costly, more environmentally friendly treatment agents is an important research direction in this area.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for preparing a water body defluorinating agent by using waste concrete, which solves the problem of high cost of defluorinating by using the existing chemical agents and solves the problem of secondary pollution of the waste concrete.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a water body defluorinating agent comprises the steps of taking waste concrete as a raw material, carrying out primary crushing and calcination, screening out set cement, carrying out powder selection and separation on the set cement after ball milling, and collecting particles with the particle size of below 80 mu m to obtain the water body defluorinating agent.
Preferably, the particle size of the waste concrete after the preliminary crushing is 10mm or less. The smaller the particle size of the concrete after the initial crushing, the more favorable the calcination to screen out the set cement from the concrete.
Preferably, the calcination conditions are: heating to 200-400 ℃ at the speed of 3-8 ℃/min, keeping the temperature for 10-30 min, and then naturally cooling. The bonding strength of aggregate and set cement in the waste concrete can be weakened through calcination, so that the set cement can be screened out from the concrete, the muffle furnace can be adopted for calcination, and the electromagnetic oscillation crusher can be adopted for oscillation separation after calcination.
Preferably, the surfactant is added during the cement ball milling process. The ball milling can further increase the microstructure defects of the set cement, increase the surface area of the set cement, and improve the ball milling effect by adding the surfactant.
Preferably, the surfactant is at least one of lignosulfonate, ethylene glycol and triisopropanolamine, wherein the addition amounts of the lignosulfonate, the ethylene glycol and the triisopropanolamine are respectively 0.06-0.1%, 0.02-0.1% and 0.03-0.1% of the mass of the set cement.
Preferably, the ball milling time is 20-50 min.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention separates cement from waste concrete and grinds the cement to prepare the water body defluorinating agent, wherein, the main composition of the cement screened from the waste concrete is hydrated calcium silicate gel (C-S-H), ettringite (AFt) and unhydrated dicalcium silicate (C-S-H)2S) and the like. Under the condition of water saturation, the C-S-H gel has a very large specific surface area, and after ball milling dispersion, microscopic defects are increased, the specific surface area is increased, and active point positions are further increased. On one hand, the structure ensures that the hydration product of the calcium-containing cement is easy to interact with water molecules, so that calcium ions are dissolved out to enter into the fluorine-containing water solution and to be mixed with F in the fluorine-containing wastewater-Combined to form CaF precipitate which is separated out from the fluorine-containing wastewater; on the other hand, F in the fluorine-containing wastewater-The fluorine ions are easy to adsorb on the surface of the C-S-H gel and then removed by subsequent filtration, and under the action of the two aspects, the fluorine ions in the water can be effectively removed.
2. The method for preparing the water body defluorinating agent by using the waste concrete has the advantages of wide raw material source and low cost, and provides a new way for resource utilization of a large amount of waste concrete; also provides a process method which is simple and convenient to operate, wide in application range, low in cost, green and environment-friendly and can treat toxicity by waste for the treatment of fluoride-containing wastewater of rivers, lakes, industry, life and the like in China; the method meets the strategic requirements of national development cycle economy, enjoys the support of national and local related industrial policies, and has wide development and application prospects.
3. The invention widens the application of the waste concrete as the building waste to the field of fluorine-containing wastewater treatment, prepares the water body fluorine removal material, has high reaction speed in the water body fluorine removal process, does not have limit mixing amount, has high utilization efficiency and stable fluorine removal effect, can be operated at room temperature, improves the resource utilization efficiency of the waste set cement, provides a technical path for the high added value utilization of the hardened set cement in the waste concrete, and avoids the problems of high porosity, high water absorption, low strength, limited mixing amount and the like in the process of preparing recycled concrete materials, building blocks or calcining cement clinker again by the waste concrete in the prior art.
Drawings
FIG. 1 is a diagram showing the fluorine removal effect of the fluorine removal agent for water prepared in example 2;
FIG. 2 is a scanning electron microscope image of the water defluorinating agent particles prepared in example 2;
FIG. 3 is an EDS (EDS) spectrum of a micro-area composition of a water body fluorine removal agent prepared in example 2 before fluorine removal;
FIG. 4 is the micro-domain analysis (EDS) spectrum of the precipitate after the fluorine removal by the fluorine removal agent for water prepared in example 2.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
In this embodiment, the method for preparing the water defluorinating agent by using the waste concrete includes the following steps:
(1) selecting waste concrete from construction waste, carrying out primary crushing by using a small hammer crusher, controlling the particle size d of the waste concrete after the primary crushing by using a square hole sieve to be less than or equal to 10mm, and loading the waste concrete after the primary crushing into a muffle furnace for low-temperature pre-calcination to weaken the bonding strength of aggregate and cement stone in the waste concrete, wherein the concrete calcination conditions are as follows: heating to 250 deg.C at a rate of 6 deg.C/min, holding the temperature for 20min, and naturally cooling to 25 deg.C.
(2) Carrying out vibration treatment on calcined waste concrete in an electromagnetic vibration crusher to separate coarse aggregate from waste set cement, adding the set cement obtained by separation into a ball mill for grinding to further increase the microstructure defects and increase the specific surface area, and adding ethylene glycol with the mass of 0.06% of the set cement into the grinding process to carry out surface dispersion treatment in order to improve the grinding effect; meanwhile, the ball milling time is controlled to be 40 min.
(3) The ground materials will generate 'split phase' due to different physical properties, the air classifier is used for powder selection and separation, and particles with the particle size less than or equal to 80 mu m are collected to obtain the water body defluorinating agent.
Example 2
In this embodiment, the method for preparing the water defluorinating agent by using the waste concrete includes the following steps:
(1) selecting waste concrete from construction waste, carrying out primary crushing by using a small hammer crusher, controlling the particle size d of the waste concrete after the primary crushing by using a square hole sieve to be less than or equal to 10mm, and loading the waste concrete after the primary crushing into a muffle furnace for low-temperature pre-calcination to weaken the bonding strength of aggregate and cement stone in the waste concrete, wherein the concrete calcination conditions are as follows: heating to 400 ℃ at the speed of 8 ℃/min, keeping the temperature for 20min, and naturally cooling to 20 ℃.
(2) Carrying out vibration treatment on calcined waste concrete in an electromagnetic vibration crusher to separate coarse aggregate from waste set cement, adding the set cement obtained by separation into a ball mill for grinding to further increase the microstructure defects and increase the specific surface area, and adding lignosulfonate accounting for 0.08 percent of the mass of the set cement, ethylene glycol accounting for 0.06 percent of the mass of the set cement and triisopropanolamine accounting for 0.06 percent of the mass of the set cement in the grinding process for carrying out surface dispersion treatment in order to improve the grinding effect; meanwhile, the ball milling time is controlled to be 30 min.
(3) The ground materials can generate 'split phase' due to different physical properties, the air classifier is used for powder selection and separation, and particles with the particle size less than or equal to 80um are collected to obtain the water body fluorine removal agent.
Fig. 2 is a microscopic scanning electron microscope image of the water body fluorine removal agent particles prepared in example 2, and it can be seen from the image that the particle size of the water body fluorine removal agent particles prepared in the present invention is about 10 μm, and the surface is formed into an irregular network shape by mutually interpenetrating and lapping a large number of micro scale-like and short column-like cement hydration products, which is loose and porous, increases the specific surface area, and further increases the active point sites, which is also the reason why the water body fluorine removal agent prepared in the present invention can effectively remove fluorine ions in water. Table 1 shows the chemical composition of the water defluorinating agent prepared in example 2.
TABLE 1 chemical composition (w) of water defluorinating agent preparedt%）
| SiO2 | CaO | Al2O3 | Fe2O3 | MgO | K2O | NaO | SO3 | TiO2 |
| 48.8295 | 30.7955 | 8.9764 | 3.8741 | 1.5689 | 1.6376 | 1.0428 | 2.0102 | 0.7680 |
Defluorination experiment:
the water body fluorine removal agent prepared in the example 2 is subjected to a simulated fluorine removal experiment, which specifically comprises the following steps:
a certain amount of analytically pure NaF is weighed accurately and 200mg/l of fluorine-containing simulated wastewater is prepared by using a volumetric flask. 100ml of the fluorine-containing simulated wastewater was sequentially weighed by a measuring cylinder into 6 clean beakers, and 0.5g, 1.0g, 2.0g, 3.0g, 4.0g and 5.0g of the water body fluorine removal agent prepared in example 2 were sequentially added to the beakers, and a magnetic stirrer was used to perform a fluorine removal reaction. And controlling the stirring strength to be 200r/min in the defluorination process, taking down the reaction product from the magnetic stirrer after reacting for 30min at room temperature, standing for 12 h and filtering.
According to the method specified in national standard of the people's republic of China, "determination of Water quality fluoride ion Selective electrode method (GB 7484-1987)", the concentration of the fluorine ions in the filtrate is determined by adopting a fluorine ion selective electrode so as to represent the actual use effect of the prepared water body fluorine removal agent, and the experimental result is shown in figure 1.
As can be seen from FIG. 1, when the dosage of the water body fluorine removal agent is 0.5g, the fluorine-containing concentration of the treated wastewater is 21mg/l, when the dosage is 1g, the fluorine-containing concentration of the treated wastewater is 20mg/l, when the dosage is increased to 2g, the fluorine-containing concentration of the treated wastewater is 10mg/l, when the dosage is continuously increased to 5g, the fluorine-containing concentration of the treated wastewater is only 5mg/l, and the water body fluorine removal agent prepared by the method can effectively remove fluorine ions in the wastewater.
And (3) drying the filtered filter residue in vacuum at 105 ℃, and performing EDS (electron-discharge spectroscopy) test on a dried sample to analyze the defluorination mechanism of the water body defluorinating agent prepared by the invention, wherein the figures 3 and 4 are respectively energy spectrum (EDS) analysis diagrams of the water body defluorinating agent before and after reaction. As can be seen from the figure, compared with the water body before the reaction, obvious fluorine element diffraction peaks appear in the X-ray energy spectrum (EDS) on the surfaces of the fluorine removing agent particles in the water body after the reaction, which indicates F in the solution after the reaction-Adsorbed or deposited on the surface of the fluorine-removing material in the form of calcium fluoride, thereby being removed from the solution.
The above examples of the present invention are merely illustrative of the present invention and are not intended to limit the embodiments of the present invention. Variations and modifications in other variations will occur to those skilled in the art upon reading the foregoing description. Not all embodiments are exhaustive. All obvious changes and modifications of the present invention are within the scope of the present invention.
Claims (1)
1. The application of the waste concrete in the water body defluorinating agent is characterized in that the preparation method of the water body defluorinating agent comprises the following steps: (1) selecting waste concrete from construction waste, carrying out primary crushing by using a small hammer crusher, controlling the particle size d of the waste concrete after the primary crushing by using a square hole sieve to be less than or equal to 10mm, and loading the waste concrete after the primary crushing into a muffle furnace for low-temperature pre-calcination to weaken the bonding strength of aggregate and cement stone in the waste concrete, wherein the concrete calcination conditions are as follows: heating to 400 ℃ at the speed of 8 ℃/min, keeping the temperature for 20min, and naturally cooling to 20 ℃;
(2) carrying out vibration treatment on calcined waste concrete in an electromagnetic vibration crusher to separate coarse aggregate from waste set cement, adding the set cement obtained by separation into a ball mill for grinding to further increase the microstructure defects and increase the specific surface area, and adding lignosulfonate accounting for 0.08 percent of the mass of the set cement, ethylene glycol accounting for 0.06 percent of the mass of the set cement and triisopropanolamine accounting for 0.06 percent of the mass of the set cement in the grinding process for carrying out surface dispersion treatment in order to improve the grinding effect; meanwhile, the ball milling time is controlled to be 30 min;
(3) the ground materials can generate 'split phase' due to different physical properties, the air classifier is used for powder selection and separation, and particles with the particle size less than or equal to 80um are collected to obtain the water body fluorine removal agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710867027.4A CN107522276B (en) | 2017-09-22 | 2017-09-22 | Preparation method of water defluorinating agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710867027.4A CN107522276B (en) | 2017-09-22 | 2017-09-22 | Preparation method of water defluorinating agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107522276A CN107522276A (en) | 2017-12-29 |
| CN107522276B true CN107522276B (en) | 2020-04-07 |
Family
ID=60737278
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710867027.4A Active CN107522276B (en) | 2017-09-22 | 2017-09-22 | Preparation method of water defluorinating agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107522276B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109675517A (en) * | 2018-12-11 | 2019-04-26 | 西安建筑科技大学 | A kind of high temperature modified high alumina cement de-fluoridation adsorbent, preparation method and applications |
| CN109652081B (en) * | 2019-01-24 | 2020-08-25 | 长江师范学院 | Preparation method of acid soil conditioner |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5349859A (en) * | 1976-10-19 | 1978-05-06 | Hitachi Chem Co Ltd | Method of treating waste liquid containing fluorine |
| CN103071450A (en) * | 2013-01-16 | 2013-05-01 | 河海大学 | Defluorination adsorbent as well as preparation method and application thereof |
| CN203922951U (en) * | 2014-07-01 | 2014-11-05 | 广东梅雁吉祥水电股份有限公司 | A kind of fluorine-contained wastewater treatment system |
| CN106365281A (en) * | 2016-10-24 | 2017-02-01 | 长江师范学院 | Preparation method of water phosphate removing agent and water phosphate removing method |
-
2017
- 2017-09-22 CN CN201710867027.4A patent/CN107522276B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5349859A (en) * | 1976-10-19 | 1978-05-06 | Hitachi Chem Co Ltd | Method of treating waste liquid containing fluorine |
| CN103071450A (en) * | 2013-01-16 | 2013-05-01 | 河海大学 | Defluorination adsorbent as well as preparation method and application thereof |
| CN203922951U (en) * | 2014-07-01 | 2014-11-05 | 广东梅雁吉祥水电股份有限公司 | A kind of fluorine-contained wastewater treatment system |
| CN106365281A (en) * | 2016-10-24 | 2017-02-01 | 长江师范学院 | Preparation method of water phosphate removing agent and water phosphate removing method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107522276A (en) | 2017-12-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110759680B (en) | Red mud utilization method based on cooperative treatment of industrial tail gas, sewage treatment and green high-performance civil functional material | |
| CN107540041B (en) | Application of waste concrete in water body defluorination | |
| CN106365281B (en) | A kind of water body dephosphorized dose of preparation method and water body dephosphorized method | |
| US11332380B2 (en) | Method for aluminum-enhanced dealkalization of red mud and separation and recovery of aluminum and iron | |
| CN107694512B (en) | Preparation method of heavy metal ion remover | |
| CN110627391B (en) | High-activity anhydrous phosphogypsum cementing material and preparation method thereof | |
| CN109621925B (en) | Carbon dioxide trapping agent and application thereof | |
| CN112608043B (en) | High-strength nickel slag-based solid waste cementing material and preparation method thereof | |
| CN108746187A (en) | A kind of harmless, the recycling restorative procedure of chromium-polluted soil | |
| Chen et al. | Comparative analysis of colloid-mechanical microenvironments on the efficient purification of phosphogypsum | |
| CN104083945A (en) | Zeolite ceramic prepared by utilizing coal gangue and construction waste and preparation technology thereof | |
| CN104772106A (en) | Synthesis method of magnetic porous ceramsite based on pulverized coal ash magnetic bead | |
| Chen et al. | Micromicelle-mechanical coupling method for high-efficiency phosphorus removal and whiteness improvement of phosphogypsum | |
| CN107522276B (en) | Preparation method of water defluorinating agent | |
| CN107188506A (en) | A kind of electrolytic manganese slag brick and its preparation technology | |
| CN107382253A (en) | A kind of greenly polymer gelled material and preparation method thereof | |
| Li et al. | Progress in comprehensive utilization of electrolytic manganese residue: a review | |
| Xiang et al. | Synergistic removal of phosphorus and fluorine impurities in phosphogypsum by enzyme-induced modified microbially induced carbonate precipitation method | |
| CN105693125B (en) | A kind of sulphate aluminium cement heat stabilizer and its application method | |
| CN108793964B (en) | Ancient building ceramic prepared from municipal sludge and preparation method thereof | |
| CN109695059B (en) | Preparation method of gypsum whisker | |
| Wang et al. | Characteristic contaminant removal purification and high value ecological utilization technology of calcination modified manganese residue | |
| Cui et al. | Utilizing microbial-induced carbonate precipitation technology and carbonation for recycling municipal solid waste incineration fly ash in the production of bricks | |
| CN116332535A (en) | Method for producing active micro powder by cooperatively treating manganese slag by using fluidized bed furnace | |
| CN107469763B (en) | Method for preparing water body defluorination material by utilizing steam pressurized concrete building block |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240409 Address after: 9-2, Building 2, No. 28 Gang'an Second Road, Jiangbei District, Chongqing, 400025 Patentee after: Chongqing Tianshuo Environmental Protection Industry Co.,Ltd. Country or region after: China Address before: No. 16, Fuling District, Chongqing, Chongqing Patentee before: YANGTZE NORMAL University Country or region before: China |